1. Field Of The Invention
The invention relates to a catalytic process of alkoxylating active-hydrogen compounds, to the starting compositions and to the alkoxylation catalysts.
2. Background Art
Hino, Makoto, and Kazushi Arata, "Synthesis of Solid Superacid Catalyst with Acid Strength of H.sub.0 &lt;-16.04", J.C.S. Chem. Comm., (1980) pages 851 and 852, discloses a solid superacid catalyst with an acid strength of H.sub.0 &lt;-16.04. The catalyst was obtained by exposing Zr(OH).sub.4, prepared by the hydrolysis of ZrOCl.sub.2, to 1N H.sub.2 SO.sub.4 and then calcining it in air at 575.degree. to 650.degree. C.
Hino, Makoto, and Kazushi Arata, "Synthesis Of Esters From Acetic Acid With Methanol, Ethanol, Propanol, Butanol, And Isobutyl Alcohol Catalyzed By Solid Superacid", Chemical Letters, Chem. Soc. Jap., (1981), pages 1671 and 1672, discloses catalytically esterifying acetic acid with lower alkanols, such as, ethanol. A solid superacid catalyst, which was obtained by exposing Zr(OH).sub.4 to 1N H.sub.2 SO.sub.4 and then calcining in air at 500.degree. to 750.degree. C., was stated to be highly active for the heterogeneous esterification reactions at 30.degree. to 45.degree. C. The reactions with used catalysts gave identical results with those using freshly activated catalysts. (Esterification reactions are known to be catalyzed by acids.) Solid superacid catalysts were also prepared from Fe(OH).sub.3 and H.sub.4 TiO.sub.4.
Hino, M., and K. Arata, "Conversion Of Pentane To Isopentane And Isopentane To Isobutane Catalyzed By A Solid Superacid In The Vapor Phase", React. Kinct. Catal. Lett., Vol. 19, No. 1-2, (1982), pages 101 to 104, discloses converting pentane and isopentane, respectively, into isopentane and isobutane using a solid superacid, which was prepared by exposing Zr(OH).sub.4 to 1N H.sub.2 SO.sub.4, followed by calcination at 650.degree. C. in air. The selectivities were 84 percent under short contact conditions at 80.degree. C. The reactions involved the isomerization and hydrocracking of lower hydrocarbons. The paper states that Takahashi et al. prepared solid superacids by supporting SbF.sub.5 on metal oxides and studied reactions of pentane and isopentane. [R. Ohnishi T., Morikawa, Y. Hiraga and K. Tanabe, Zeitschrift fur Physikalische Chemic Nue Folg, Vol. 130, pp. 205-209, (1982)]
The above-discussed Hino and Arata articles are inconsistent and teach away from the invention which is the subject of this application.
Chukhlantsev, V. G., and Yu. M. Galkin, "Thermal Decomposition Of Basic Zirconium Sulphate", Russian Journal of Inorganic Chemistry, 18 (6), (1973), pages 770 and 771, earlier disclosed that when basic zirconium sulphate is heated to 500.degree. to 650.degree. C. (even above 400.degree. to 420.degree. C.) only dehydration, accompanied by the formation of an anhydrous product amorphous to X-rays, took place. Starting from 600.degree. C. the latter decomposed with the formation of ZrO.sub.2 and release of SO.sub.3. Basic zirconium sulfate was obtained by boiling a solution of zirconium oxide chloride containing 50 g of ZrO.sub.2 per liter, 15 g of free HCl per liter, and sulfuric acid to give SO.sub.3 : ZrO.sub.2 =0.56 (molar). The product was washed and then dried at 100.degree. C.
The Condensed Dictionary, 10th Ed., (1981) pages 1115 to 1117, discloses: Zr.sub.5 O.sub.8 (SO.sub.4).sub.2 .multidot.xH.sub.2 O, zirconyl sulfate on zirconium sulfate, basic; ZrOCO.sub.3 .multidot.xH.sub.2 O, zirconyl carbonate or zirconium carbonate, basic; ZrOCl.sub.2 .multidot.8H.sub.2 O, zirconyl chloride or zirconium oxychloride; ZrO(OH)Cl.multidot..sub.n H.sub.2 O, zirconyl hydroxychloride; and ZrO(OH)NO.sub.3, zirconyl hydroxynitrate or zirconyl nitrate, basic. Zirconium oxychloride can be prepared by the action of hydrochloric acid on zirconium oxide. Zirconyl sulfate can be prepared in a similar manner. Zr(OH).sub.4 can be prepared by the action of a solution of sodium hydroxide on a solution of a zirconium salt.
Ethylene oxide, also termed oxirane, has been reacted with C.sub.2 H.sub.5 OH to produce C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OH. The same reaction with ethylene sulfide is known.